Method for marking sites

ABSTRACT

A method for determining changes of a site, wherein the site is treated with an aqueous dispersion having at least one binder, at least one substance emitting visible light on UV exposure, at least one binder and, optionally, a dispersant and the site thus treated and/or untreated adjacent sites are exposed to UV light and the deviation of the light intensity of the emitted light of a partial area of the site from the mean light intensity of the emitted light of the site area and/or the light intensity of the emitted light of a part of the adjacent, untreated area from the mean light intensity of the emitted light of the adjacent untreated areas and/or the light intensity of the emitted light of the site immediately after the treatment with the composition from the light intensity of the emitted light at a later time and/or the light intensity of the emitted light of the adjacent untreated area immediately after the treatment of the site with the composition from the light intensity of the emitted light of the adjacent, untreated area at a later time are determined.

This application is a Divisional of U.S. patent application Ser. No.10/817,985 filed Apr. 5, 2004, entitled “Method for Marking Sites”, thecontents of which are hereby incorporated by reference in theirentirety.

The present invention relates to a method for marking sites, inparticular for the purpose of determining access on foot, access byvehicle and/or other manipulations.

The use of the abovementioned method relates primarily to areas whichcan be completely monitored only at high cost, for example by a largenumber of guards, or protected by expensive fences. The method accordingto the invention is distinguished by wide applicability and highflexibility. In addition few personnel are required for the methodaccording to the invention.

The invention relates to a method for determining changes of a site,which is characterized in that

-   a) the site is treated with a composition and-   b) the site thus treated and/or the untreated areas adjacent thereto    are exposed to UV light and the deviation    -   b1) of the light intensity of the emitted light of a partial        area of the site from the mean light intensity of the emitted        light of the site area and/or    -   b2) the light intensity of the emitted light of a part of the        adjacent, untreated area from the mean light intensity of the        emitted light of the adjacent untreated areas and/or    -   b3) the light intensity of the emitted light of the site        immediately after the treatment with the composition from the        light intensity of the emitted light at a later time and/or    -   b4) the light intensity of the emitted light of the adjacent        untreated area immediately after the treatment of the site with        the composition from the light intensity of the emitted light of        the adjacent, untreated area at a later time        are determined,        the composition being an aqueous dispersion comprising:-   a1) at least one binder,-   a2) at least one substance emitting visible light on UV exposure and-   a3) optionally a dispersant.

Aqueous polymer formulations which contain substances which emit visiblelight on UV exposure have long been known in various applications.

DE-A 19 521 500 describes an aqueous dispersion comprising awater-dispersible polyurethane and a fluorescent dye as a coatingmaterial for greenhouse sheets.

U.S. Pat. No. 3,995,157 describes a method for discovering damage(breaks, cracks, etc.) in metallic objects which functions by means ofapplying a coating consisting of a polymeric material and a compoundfluorescing on UV exposure.

The composition preferably contains polymeric film-forming compounds asbinders of component a1).

Binders of component a1) can be prepared by polymerization in aqueoussolution, such as, for example, acrylamido homo- and copolymers, whichare described in Houben-Weyl, Methoden der organischen Chemie [Methodsof organic chemistry], 4th Edition, Volume E 20, Part 2, pages1178-1191. Examples of suitable comonomers for acrylamide andmethacrylamide are: styrene, acrylic acid and methyl, ethyl, butyl and2-ethylhexyl (meth)acrylate, either alone or as a mixture of a pluralityof comonomers. The comonomers are used in numerical ratios which areknown to a person skilled in the art.

Emulsion polymers as described in Houben-Weyl, Methoden der organischenChemie [Methods of organic chemistry], 4th Edition, Volume E 20, Part 2,pages 1150 to 1155, are furthermore suitable as products of thecopolymerization of methyl, ethyl, butyl and 2-ethylhexyl (meth)acrylatewith styrene, acrylonitrile, acrylic acid, acrylamide andmethacrylamide, either alone or as a mixture with a plurality ofcomonomers.

Copolymers, such as water-soluble styrene/acrylic acid or methyl, ethyl,butyl and 2-ethylhexyl (meth)acrylate, as described in Houben-Weyl,Methoden der organischen Chemie [Methods of organic chemistry], 4thEdition, Volume E 20, Part 2, page 985, and styrene/maleic acidcopolymers, which are described in the same reference, are alsosuitable.

Preferred binders of component a1) are polyurethanes, as described inHouben-Weyl, Methoden der organischen Chemie [Methods of organicchemistry], 4th Edition, Volume E 20, Part 1, pages 1659 to 1681.

Particularly preferred polyurethanes as binders of component a1) arethose which are dispersible in water itself and are prepared from:

-   i) diisocyanates comprising 4 to 50 carbon atoms,-   ii) diols having a molecular weight of 500 to 4000 g/mol,-   iii) diols and/or di- and triamines as chain extenders having a    molecular weight of 62 to 500 g/mol,-   iv) mono- and polyols and/or mono- and polyamines having primary    and/or secondary amino groups, which also have a group having a    hydrophilizing effect.

Examples of suitable diisocyanates i) are: tetramethylene diisocyanate,hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylenediisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate,tetradecamethylene diisocyanate, trimethylhexane diisocyanate ortetramethylhexane diisocyanate, cycloaliphatic diisocyanates, such as1,4-, 1,3- or 1,2-diisocyanatocyclohexane,4,4′-di(isocyanatohexyl)methane,1-isocyanato-3,3,5-trimethyl-5-(isocyanatomethyl)-cyclohexane(isophorone diisocyanate) or 2,4- or2,6-diisocyanato-1-methylcyclohexane, and aromatic diisocyanates, suchas 2,4- or 2,6-toluene diisocyanate, tetramethylxylylene diisocyanate,p-xylylene diisocyanate, 2,4′- or 4,4′-diisocyanatodiphenylmethane, 1,3-or 1,4-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate,1,5-naphthylene diisocyanate, diphenylene 4,4′-diisocyanate,4,4′-diisocyanato-3,3′-dimethylbiphenyl, 3-methyldiphenylmethane4,4′-diisocyanate or diphenyl ether 4,4′-diisocyanate. Mixtures of saiddiisocyanates may also be present.

Preferred diisocyanates (i) are the industrial polyisocyanates customaryin polyurethane chemistry, such as hexamethylene diisocyanate,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophoronediisocyanate, IPDI), perhydro-4,4′-diphenylmethane diisocyanate, 2,4-and 2,6-toluene diisocyanate and any desired mixtures of these isomers,diphenylmethane 4,4′-diisocyanate and mixtures thereof with thecorresponding 2,2′- and 2,4′-isomers.

The abovementioned aliphatic polyisocyanates are particularly preferred.

The diols ii) have an average molecular weight of 500 to 4000 g/mol,preferably of 500 to 3000 and particularly preferably of 700 to 3000g/mol and have a functionality of 2.

Polyesterdiols (ii) are prepared by reacting polyhydric alcohols withdibasic carboxylic acids. Instead of the carboxylic acids, carboxylicanhydrides may also be used. Both aliphatic and cycloaliphatic, andaraliphatic and aromatic dicarboxylic acids can be used. Moreover,heterocyclic, unsaturated or substituted (for example by halogen atoms)dicarboxylic acids may be used. The following may be mentioned by way ofexamples of these: malonic acid, succinic acid, glutaric acid, adipicacid, pimelic acid, suberic acid, azelaic acid, sebacic acid,nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylicacid, phthalic acid, isophthalic acid, terephthalic acid, phthalicanhydride, tetrahydrophthalic anhydride, glutaric anhydride, succinicanhydride, maleic acid, maleic anhydride, fumaric acid and dimeric fattyacids.

Preferred dicarboxylic acids are those which have 2 to 20 carbons takinginto account the carboxyl carbons.

Examples of suitable polyhydric alcohols are: ethylene glycol,propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, butene-1,4-diol,butyne-1,4-diol, pentane-1,5-diol, neopentylglycol, diethylene glycol,triethylene glycol, tetraethylene glycol, polyethylene glycols,dipropylene glycol, tripropylene glycol, polypropylene glycols,dibutylene glycol and also polybutylene glycols.

Ethylene glycol, butane-1,4-diol, hexane-1,6-diol, neopentylglycol,octane-1,8-diol and dodecane-1,12-diol are preferred.

In addition, reaction products of the diols listed above with phosgeneor their transesterification products with carbonic esters, such as, forexample, diphenyl carbonate, can likewise be used as polyesterdiols(ii).

Bishydroxy-functional products of the ring-opening polymerization ofcyclic esters, such as, for example, of butyrolactone or caprolactone,can also be used as polyesterdiols (ii).

Polyetherdiols (ii) are obtainable, for example, by reaction of ethyleneoxide, propylene oxide, styrene oxide and/or butylene oxide with wateror with other low molecular weight initiator molecules, such as, forexample, ethylene glycol, propane-1,2-diol, propane-1,3-diol,butane-1,4-diol, butene-1,4-diol, butyne-1,4-diol, pentane-1,5-diol,neopentylglycol, diethylene glycol, triethylene glycol, tetraethyleneglycol, polyethylene glycols, dipropylene glycol, tripropylene glycol,polypropylene glycols, dibutylene glycol and also polybutylene glycols,by known processes of the prior art.

Where the field of use requires a biodegradable polyester dispersion,polyesterdiols are preferred as diols (ii).

Polyols (iii) which are suitable as chain extenders, optionally also ascrosslinking agents, are, for example, low molecular weight polyhydricalcohols having a molecular weight range from 62 to 400 g/mol. Thefollowing diols may be used: ethylene glycol, propane-1,2-diol,propane-1,3-diol, butane-1,4-diol, butene-1,4-diol, butyne-1,4-diol,pentane-1,5-diol, neopentylglycol, diethylene glycol, triethyleneglycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol,tripropylene glycol, polypropylene glycols, dibutylene glycol and alsopolybutylene glycols.

Ethylene glycol, butane-1,4-diol, hexane-1,6-diol, neopentylglycol,octane-1,8-diol and dodecane-1,12-diol are preferred.

If branching is desired, it is also possible to use polyols having ahigher functionality, such as, for example, trimethylolpropane,glycerol, pentaerythritol, sorbitol or sucrose.

Di- or triamines can be employed as amines (iii) which can be used aschain extenders, optionally also as crosslinking agents. Thesepreferably have a molecular weight of 60 to 300 g/mol and are used,especially in crosslinking and/or chain extension, in water. Forexample, the following are suitable: 1,4-diaminobenzene, 2,4- and2,6-diaminotoluene, 2,4′- and/or 4,4′-diaminodiphenylmethane,1,4-diaminobutane, 1,6-diaminohexane, ethylenediamine and its homologs,isophoronediamine, bis(4-aminocyclohexyl)-methane,1,4-diaminocyclohexane, hydrazine, hydrazine hydrate and piperazine.

An example of the trifunctional amines is diethylenetriamine.

Particularly preferred diamines are aliphatic types, such as, forexample, 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine,bis-(4-aminocyclohexyl)-methane, 1,4-diaminocyclohexane, ethylenediamineand its homologs and piperazine.

The less preferred diamines include compounds such as2,4-diaminomesitylene, 1,3,5-triethyl-2,4-diaminobenzene,1,3,5-triisopropyl-2,4-diaminobenzene,1-methyl-3,5-diethyl-2,4-diaminobenzene, the industrial mixtures thereofwith 1-methyl-3,5-diethyl-2,6-diaminobenzene,4,6-dimethyl-2-ethyl-1,3-diaminobenzene,3,5,3′,5′-tetraethyl-4,4′-diaminodiphenylmethane,3,5,3′,5′-tetraisopropyl-4,4′-diaminodiphenylmethane or3,5-diethyl-3′,5′-diisopropyl-4,4′-diaminodiphenylmethane.

Any desired mixtures of such diamines may also be used.

Polyols and/or polyamines (iv) having primary and/or secondary aminogroups, which also have a group having a hydrophilizing effect, are usedfor ensuring the water dispersibility of the polyurethane.

The amount to be used of groups having a hydrophilizing effect is knownto a person skilled in the art; the amount which ensures sufficientwater dispersibility of the polyurethane is always used.

Examples of suitable groups having a hydrophilizing effect are:

-   a) nonionic structures of the general formula (I):    R¹O—(CHX—CHY—O)_(n)—CHX—CHY—Z—  (I)    -   in which    -   n represents a number from 3 to 70,    -   X and Y denote hydrogen or methyl, and, where one of the        radicals X or Y represents methyl, the other must be hydrogen,    -   R¹ denotes a straight-chain or branched C₁-C₆-alkyl radical or        straight-chain or branched C₁-C₆-acyl radical, it furthermore        being possible for R¹ also to form a cyclic —(CH₂)_(m)-alkylene        radical with m=4, 5, 6 or 7, in which one or two CH₂ groups can        be replaced by O and/or NH, and/or one or two CH₂ groups can be        substituted by methyl, and    -   Z represents O, S or NH and ensures connection to the        polyurethane;

b) cationic structures of the general formula (II):R²R³[NXY]⁺  (II

-   -   in which    -   X and Y denote hydrogen or methyl and    -   R² and R³ represent straight-chain or branched alkyl radicals,        via which the connection to the cationic polyurethane is        ensured;

-   c) anionic structures from the group consisting of: sulphonate,    carboxylate, phosphate in the form of their alkali metal and/or    ammonium salts.

Particularly suitable mono- and polyols and/or mono- and polyamines (iv)having nonionic groups are polyethylene glycol monoalkyl ethers, whichare advantageously used in the preparation of the polyurethane andbefore the dispersing and act as chain terminators.

Polyethylene glycol monomethyl ethers are particularly preferred.

Examples of particularly suitable mono- and polyamines (iv) havingpotentially cationic groups, which can be cationized by protonation withacids and/or quaternization by means of alkylating agents, areN,N-bishydroxyalkylalkylamine, N-alkyldialkanolamines,trishydroxyalkylamines, N,N-dialkylalkylamines, dialkyl alcohols; here,the alkyl radicals must comprise one to four carbon atoms.

N-Methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine,dimethylethanolamine, diethylethanolamine and triethanolamine areparticularly preferred.

Examples of particularly suitable mono- and polyols and/or mono- andpolyamines (iv) having potentially anionic groups, which can beanionized by salt formation with ammonia or alkali metal hydroxides,carbonates and/or bicarbonates, are mono- and dihydroxycarboxylic acids,mono- and diaminocarboxylic acids, mono- and diaminosulphonic acids andmono- and dihydroxysulphonic acids.

Lactic acid, dimethylolpropionic acid, glycocoll, taurine and2-(2-aminoethyl)ethanesulphonic acid are particularly preferred.

The preparation of the dispersions is effected, for example, accordingto the rules of the prior art (Houben-Weyl, Methoden der organischenChemie [Methods of organic chemistry], 4th Edition, Volume E 20, Part 1,pages 1659 to 1681), either by the acetone method or by the meltdispersion method.

The hydroxy-functional components (iv) can advantageously beincorporated into the polyurethane prior to dispersing, and theamino-functional components (iv) are expediently added to the dispersingwater in the preparation of the dispersion.

In the case of components (iv) containing potentially cationic groups,the dispersing water is acidified according to the content of component(iv) in the polyurethane; in the case of potentially anionic components(iv), alkali is added to the dispersing water according to the contentof the component (iv) in the polyurethane.

Examples of a suitable substance b) emitting visible light on UVexposure are optical brighteners, also referred to as fluorescentwhitening agents. The optical brighteners which can be used for thepurpose according to the invention preferably absorb light in awavelength from 1 nm to 420 nm, preferably 200 to 420 nm, and emit lightpreferably in the wavelength interval between 360 and 830 nm. The mainabsorption peak is at a lower wavelength than the main emission peak.

A mixture according to the invention preferably contains 0.001 to 20% byweight, preferably 0.01 to 10% by weight, of the optical brightener.

The optical brighteners which can preferably be used for the applicationaccording to the invention belong, for example, to the followingstructure classes: polystyrylstilbenes, flavonic acid derivatives,coumarins or pyrazolines.

Polystyrylstilbenes preferably have one or more structural units of theformula (III)Ph—CH═CH—  (III).Here, Ph is intended to represent a phenyl radical.

They can be characterized in particular by the formula (IV):

in which

-   -   R⁵ denotes hydrogen, hydroxyl, SO₃M, COOM, OSO₃M or OPO(OH)OM,        and M represents hydrogen, Na, K, Ca, Mg, ammonium, mono-, di-,        tri- or tetra-C₁-C₃₀-alkylammonium, mono-, di-, tri- or        tetra-C₁-C₃₀-hydroxyalkylammonium or ammonium di- or        trisubstituted by mixtures of C₁-C₃₀-alkyl and        C₁-C₃₀-hydroxyalkyl groups, SO₂N(C₁-C₃₀-alkyl)₂,        O—(-C₁-C₃₀-alkyl), CN, Cl, COO(-C₁-C₃₀-alkyl),        CON(-C₁-C₃₀-alkyl)₂ or a C₁-C₃₀-alkyl radical,    -   R⁶ and R⁷, independently of one another, denote SO₃M, COOM,        OSO₃M or OPO(OH)OM and M has the meaning described above, x has        the value 0 or 1 and the structure (III) is trans-coplanar or        cis-coplanar.

Flavonic acid derivatives:

A preferred generally valid structure is described by the formula (V):

in which

-   -   R⁸ denotes hydrogen, R⁹ denotes a mono- or disubstituted        triazine ring and    -   W represents an anionic function, such as, for example,        carboxylate, sulphate, sulphonate or phosphate,    -   M having the above meaning.

Preferred brighteners of the formula (V) are those which correspond tothe formula (VI)

in which

-   -   R¹⁰, R¹¹ and R¹², independently of one another, denote phenoxy,        mono- or disulphonated phenoxy, phenylamino, mono- or        disulphonated phenylamino, phenylamino substituted by        C₁-C₃-alkyl, cyano, halogen, COOR, CONH—R, —NH—COR, SO₂NH—R,        O—R, morpholino, piperidino, pyrrolidino, —O-C₁-C₄-alkyl,        —NH(C₁-C₄-alkyl), —NH(C₁-C₄-alkyl)₂,        —NH-C₂-C₄-alkylene-O-C₂-C₄-alkylene-OR,        —NH(C₂-C₄-hydroxyalkyl)₂, —NHC₂-C₄-akylene-=-C₂-C₄-alkylene-OR,        an amino acid or an amino acid amide from the amino group of        which a hydrogen atom has been removed;    -   —NHCH₂CH₂OH, —N(CH₂CH₂OH)₂, —N(CH)₃CH₂CH₂OH, —NH₂, —CH₃,        —S-C₁-C₄-alkyl, —S-aryl, —Cl, —NHCH₂CH₂SO₃H, —NH(CH₂CH₂SO₃H)₂,        —N(CH₂CH₂OH)CH₂CH₂CONH₂; and R represents H or C₁-C₃-alkyl and M        has the meaning described above.

Brighteners of the formula (V) which correspond to the formula (VIII)

in which

-   -   R¹³ and R¹⁴, independently of one another, are hydrogen, phenyl,        monosulphonated phenyl, methyl, ethyl, propyl, methoxy or ethoxy        and M has the above meaning,        are likewise preferred.

Coumarins:

Preferred coumarins are, for example, those of the formula (IX):

in which radical R¹⁵ represents (CH₂)₁₋₄COOM, (CH₂)₁₋₄SO₃M, (CH₂)₁₋₄SO₄Mor (CH₂)₁₋₄OPO(OH)OM, with M as described above,

-   -   R¹⁶ represents H, phenyl, COO-C₁-C₃₀-alkyl or glucosyl,    -   R¹⁷ denotes OH or O-C₁-C₃₀-alkyl and    -   R¹⁸ denotes OH, O-C₁-C₃₀-alkyl or glycosidically bonded sugar        radicals.

Pyrazolines:

The preferred pyrazolines which can be used in the application accordingto the invention are, for example, those of the formula (X):

in which

-   -   R¹⁹ denotes hydrogen or Cl,    -   R²⁰ denotes SO₃M, COOM, OSO₃M or OPO(OH)OM, the definitions        above applying to M,    -   R²¹ and R²², independently of one another, denote hydrogen,        C₁-C₃₀-alkyl or phenyl, and    -   R²³ denotes hydrogen or Cl.

In addition to the specified optical brighteners which are colourless assubstances, it is also possible to use so-called fluorescent dyes, aspublished, for example, by H. Langhals and described in conferencevolume: DGMK-Fachbereich Kohlenveredlung [DGMK coal conversiondepartment], meeting on “Herstellung und Anwendung mehrkerniger Aromatenund Heteroaromaten [Production and use of polynuclear aromatics andheteroaromatics]”, 28 Nov. 1991 in Bochum, on pages 95 to 118, providedthat this does not impair the intended use or the natural colour on anappropriate surface is inconspicuous. The compounds mentioned there arenot preferred, however.

Preferred as substance a2) emitting visible light on UV exposure are thetriazine derivatives of flavonic acid having the following structure(XI).

in which

-   -   R²⁴, R²⁵ and R²⁶, independently of one another, represent —NH₂,        —NH—CH₃, —NH-ethyl, —NH(—CH₃)₂, —NH-(ethyl)₂, —NHCH₂CH₂OH,        —NH-C₂-C₄-hydroxyalkyl, —NH(C₂-C₄-hydroxyalkyl)₂, —NHCH₂CH₂SO₃H,        —NH—CH₂CH₂OCH₂CH₂OH, —O—CH₃, —OCH—(CH₃)₂, —O—CH₂CH₂OCH₃,        —N(CH₂CH₂OH)₂, —N(CH₂CHOH—CH₃)₂, morpholino, —S—CH₃,        —N(CH₂CH₂OH)CH₂CH₂CONH₂ or a radical of the formula        in which    -   R denotes hydrogen or C₁-C₃-alkyl and M has the meaning        described above. Likewise particularly preferred are the        triazine derivatives having the structure (XII).        in which    -   R²⁷ and R²⁸, independently of one another, denote hydrogen,        C₁-C₃-alkyl or phenyl.

The optional dispersant a3) preferably serves for better distribution ofthe essentially water-insoluble or sparingly soluble substance a2)emitting visible light on UV exposure.

In principle, all water-soluble polymeric dispersants are suitable forthis purpose.

Polyvinyl ethers and polyvinyl esters and partial or complete hydrolysisproducts of the polyvinyl esters (Houben-Weyl, Methoden der organischenChemie [Methods of organic chemistry], 4th Edition, Volume E 20, Part 2,pages 1195 to 1226), starch esters (Houben-Weyl, Methoden derorganischen Chemie [Methods of organic chemistry], 4th Edition, Volume E20, Part 3, pages 2151 to 2161) and starch ethers (Houben-Weyl, Methodender organischen Chemie [Methods of organic chemistry], 4th Edition,Volume E 20, Part 3, pages 2138 to 2147) and starch ether esters(Houben-Weyl, Methoden der organischen Chemie [Methods of organicchemistry], 4th Edition, Volume E 20, Part 3, page 2151), celluloseethers (Houben-Weyl, Methoden der organischen Chemie [Methods of organicchemistry], 4th Edition, Volume E 20, Part 3, pages 2086 to 2089) andcellulose esters (Houben-Weyl, Methoden der organischen Chemie [Methodsof organic chemistry], 4th Edition, Volume E 20, Part 3, pages 2093 to2123) and cellulose ether esters (Houben-Weyl, Methoden der organischenChemie [Methods of organic chemistry], 4th Edition, Volume E 20, Part 3,page 2092) may be mentioned by way of example.

Biodegradable water-soluble polymeric dispersants a3) are preferred.

Polyvinyl alcohol is particularly preferred.

Suitable auxiliaries and additives a4) optionally to be added to thecomposition are, for example, flow control agents, free-flow agents,pigments, antifoams, deaerators, dyes, fillers, dulling agents,thickeners, emulsifiers, levelling agents such as those known to aperson skilled in the art from the prior art.

The preparation of the composition is preferably effected by mixing thecomponents a1) to a4) in water.

The actual use can be effected, for example, by applying the compositionto the site to be monitored, preferably the traffic route, or to thatpart of the site which is to be marked. This is expediently effected byspraying with apparatuses according to the prior art. In the case ofrelatively small objects, the treatment liquor according to theinvention can also be applied by spreading, brushing on or rolling on.

As a result of spraying with the composition, a cohesive strong filmcomprising a substance emitting visible light on UV exposure forms afterdrying on the traffic routes, such as, for example, roads, carriagewaysand paths, as well as railway lines or tram lines, but also plots, suchas, for example, park, garden, woodland or other sites. Access by footand by vehicle destroys or damages this film locally in the areassubjected to stress, so that, on UV exposure, these tracks can bevisualized as defects. Thus, access by foot and/or access by vehicle andany other change can be determined.

In a particular embodiment, a composition which contains a biodegradablebinder is applied so that aftertreatment can be effected at regularintervals and “old” and “new” damage to the film cannot lead tomisinterpretations.

Thus, areas can be monitored for unauthorized access by foot and accessby vehicle without this having to be effected in a time-consuming andlabour-intensive manner. A further advantage is that detected changescan be monitored locally, and this is therefore also possible in asubstantially less labour- and hence cost-intensive manner.

The method according to the invention is used for securing danger areas,such as, for example, military areas and security areas, militarytraining grounds, public buildings and the immediate vicinity thereof,strategically important means of transport, such as bridges andcrossings, locks, ship lifts and waterways, such as canals, railwaylines and tram lines, in particular fast and high-speed zones, andelectromagnetic railways, motorways and the immediate vicinity thereof,such as intersections and intersection-free facilities, such as motorwayinterchanges.

It is also possible to secure stocks in this way to prevent possiblemanipulations. The method according to the invention can also be usedfor securing movable objects, such as, for example, garden furniture orcar radios, but also larger warehouses and quantities of goods, such as,for example, for bulk materials, such as coal or briquettes, in a heapor loaded onto cars, but also for high-quality goods present in packedform, such as, for example, television sets or electronic appliances incartons or containers.

Here, the identification of moving objects is possible or detection onthe basis of marked packaging (for example televisions, electronicappliances) or marked containers or by means of spilt transportedmaterial (for example coal).

A further application to be mentioned here by way of example is themarking of containers for determining manipulations of fastening orother security systems. Thus, for example, cabinets, desks, crates orelse doors which are screwed together, nailed together or rivetedtogether can be marked by the method according to the invention fordetermining unauthorized opening or for revealing breaking-open.

EXAMPLES

Raw materials:

Preparation of the Polymeric Adhesive 1:

1500 parts of a polyester of adipic acid with 1,6-hexanediol andneopentylglycol (OH number 65) are prepolymerized with 265 parts ofhexamethylene diisocyanate until the isocyanate content is 3.3%. Theprepolymer is then dissolved in 3360 parts of acetone.

86 parts of 45% strength solution of 2-aminoethyl-2-aminoethanesulphonic acid sodium salt (NH₂CH₂CH₂HCH₂CH₂SO₃Na) in water, 13.5 partsof ethylenediamine and 408 parts of water are then added to the solutionin acetone and stirred in homogeneously.

After dilution with 2340 parts of water has been effected and theacetone distilled off, an approx. 40% strength dispersion results.

Optical brightener 1): Compound corresponding to structure (XII) withhydrogen as R 27 and phenyl as R 28.

Polymeric dispersant 1) Mowiol® 26-88 from Clariant.

Components of the Composition 1: 2 parts by weight of the abovementionedoptical brightener 450 parts by weight of the polymeric adhesivedescribed above 450 parts by weight of an aqueous solution containing0.05 part by weight of Mowiol ® 26-88 98 parts by weight ofdemineralized water

Component of the Composition 2: 2 parts by weight of the abovementionedoptical brightener 450 parts by weight of the polymeric adhesivedescribed above 450 parts by weight of an aqueous solution containing0.05 part by weight of Mowiol ® 26-88 20 parts by weight of ACE Matt ®OK 412 (dulling agent from Degussa) 78 parts by weight of demineralizedwater

Components of the Aqueous Composition 3: 2 parts by weight of theabovementioned optical brightener 450 parts by weight of the polymericadhesive described above 450 parts by weight of an aqueous solutioncontaining 0.05 part by weight of Mowiol ® 26-88 5 parts by weight ofAcramin ® Black FBB (a pigment formulation from Dystar) 93 parts byweight of demineralized waterTest:

The compositions 1, 2 and 3 prepared according to the abovementionedformulation were each sprayed by means of a flower spray onto a 1 m×1 msquare with track ballast, gravel or fine aggregate.

After drying of the aqueous layer, the respective layers were walked onbriefly by a test subject.

Exposure to a portable UV lamp both before and after the test surfaceshad been walked on gave a readily distinguishable difference in opticalimpression in all cases. The traces can be very readily identified.

1. A method for determining changes of a site, comprising: a) treatingthe site with a composition; b) exposing the site thus treated, anuntreated site or combinations thereof to UV light; and c) determining adeviation of an intensity of emitted light from the site immediatelyfollowing treatment and a light intensity of emitted light from the siteat a later time, wherein the composition is an aqueous dispersionhaving: a1) at least one binder is selected from a biodegradablewater-dispersable polyurethane binder, a polymeric film forming binder,and combinations thereof; a2) at least one substance that emits visiblelight upon exposure to UV light; and a3) optionally, a dispersant. 2.The method of claim 1, wherein the biodegradable, water-dispersablepolyurethane binder comprises: a diisocyanate having 4 to 50 carbonatoms; a diol having a molecular weight of 500 to 4,000 g/ml selectedfrom polyesterdiols; a diol, diamine, or triamine chain extender havinga molecular weight of 62 to 500 g/mol or a combination of diol, diamine,and triamine chain extenders; a monol, polyol, monoamine or polyaminehaving primary or secondary amino groups or combinations thereof and atleast one group having a hydrophilizing effect.
 3. The method of claim1, wherein the use of a biodegradable water dispersable polyurethaneimproves interpretability of the emitted light.
 4. The method of claim1, wherein the polymeric film forming binder is prepared bypolymerization in and aqueous solution.
 5. The method of claim 4,wherein the polymerization comprises the polymerization of a acrylomidohomo- and copolymer wherein the comonomer is selected from acrylamide;methacrylamide; styrene; acrylic acid; methyl, ethyl, butyl and2-ethylhexyl (meth)acrylate; or combinations thereof.
 6. The method ofclaim 4, wherein the polymerization comprises an emulsioncopolymerization of monomers selected from methyl, ethyl, butyl and2-ethylhexyl (meth)acrylate, and combinations thereof and monomersselected from styrene, acrylonitrile, acrylic acid, acrylamide,methacrylamide and combinations thereof.
 7. The method of claim 1,wherein movement within or around the site is observed by monitoring thedeviation over time.
 8. A site marked using the method of claim
 1. 9. Amethod for marking a site, comprising: a) treating the site with acomposition; b) exposing the site thus treated, an untreated site orcombinations thereof to UV light; c) observing emitted light from thesite so treated; and d) repeating step c) intermittently, wherein thecomposition is an aqueous dispersion having: a1) at least one binderselected from a biodegradable water-dispersable polyurethane binder,polymeric film forming binder and combinations thereof; a2) at least onesubstance that emits visible light upon exposure to UV light; and a3)optionally, a dispersant.
 10. The method of claim 9, wherein movementwithin or around the site is observed by monitoring changes in theemitted light between intermittent observations.
 11. A site marked usingthe method of claim 9.